Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
  • C08F30/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
  • C08F30/08—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/541—Silicon-containing compounds containing oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
  • C08K9/04—Ingredients treated with organic substances
  • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
  • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
  • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
  • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes

Definitions

• the present invention relates to a curable composition and its use. More specifically, the present invention relates to a curable composition, a cured product obtained by curing the composition, and an optical material / electronic material comprising the cured product.
• the material include an optical lens, an optical disk substrate, a liquid crystal display element substrate, a color filter substrate, an organic EL (Electro Luminescence) display element substrate, a solar cell substrate, a touch panel, an optical element, an optical waveguide, and an LED ( Light (Emitting) Diode)
• optical materials and electronic materials such as sealing materials.
• inorganic glass is often used as a material for forming a liquid crystal display element substrate, a color filter substrate, an organic EL display element substrate, a solar cell substrate, a touch panel, and the like.
• a plastic material instead of a glass plate because of problems such as the glass plate is easily broken, cannot be bent, has a large specific gravity, and is not suitable for weight reduction.
• the optical material for example, a substrate for a liquid crystal display element, is required to have high transparency because it transmits light.
• a plastic material excellent in heat resistance corresponding to lead-free solder has been demanded.
• the volume change during heating of the plastic material is small and the linear expansion coefficient is small.
• it is important that the shrinkage rate during curing is small for precise processing.
• Patent Document 1 discloses a resin composition comprising an amorphous thermoplastic resin and bis (meth) acrylate that can be cured by active energy rays. A member formed by curing is disclosed. Patent Document 1 describes that the member can be suitably used for an optical lens, an optical disk substrate, a plastic liquid crystal substrate, and the like instead of a glass substrate. However, Patent Document 1 does not discuss the shrinkage rate of the resin composition and the linear expansion coefficient of the member.
• the transparency of the member may be reduced due to the difference between the refractive index of the amorphous thermoplastic resin and the refractive index of the resin obtained by curing the bis (meth) acrylate with active energy rays. is there.
• Patent Document 2 discloses a silica-based polycondensate obtained by hydrolyzing and polycondensing a specific silane compound in a colloidal silica dispersion in methyl methacrylate or the like or a bisphenol A type ethylene oxide-modified (meth) acrylate.
• a curable composition uniformly dispersed in is disclosed.
• Patent Document 2 describes that the composition can give a cured product excellent in transparency and rigidity, and that the cured product is useful for applications such as optical material applications.
• Patent Document 2 does not discuss the shrinkage rate of the curable composition and the linear expansion coefficient of the cured product.
• a method for reducing the shrinkage rate and the linear expansion coefficient there are generally a method of adding an inorganic filler to a resin composition and a method of laminating an inorganic film on a substrate.
• an inorganic filler is added to the resin composition, the transparency of the cured product (substrate) obtained by curing the resin composition is significantly impaired, the surface smoothness is lost, and the dispersibility of the inorganic filler is poor.
• the problem of the following (2) arises because the difference in shrinkage at the time of curing between the inorganic film and the resin composition that is cured to be a substrate is large. (1) The adhesion between the inorganic film and the substrate is poor. (2) The inorganic film is peeled off from the substrate or the substrate is cracked.
• Patent Document 3 a silica-based polycondensate obtained by hydrolyzing and polycondensating a silane compound having a hydrocarbon residue having 1 to 10 carbon atoms in a colloidal silica dispersion is disclosed in (meth) acrylate.
• a curable composition is described which provides a uniformly dispersed cured product with excellent transparency and rigidity.
• the viscosity and shrinkage rate of the cured product obtained from this curable composition have not been studied.
• Patent Document 4 a silica-based condensation polymer obtained by hydrolyzing and condensation-polymerizing a specific silane compound in a colloidal silica dispersion is uniformly dispersed in a bisphenol A-type ethylene oxide-modified (meth) acrylate.
• a curable composition that gives a cured product having excellent transparency and rigidity is described.
• the organic group having an ethylenically unsaturated group of the silane compound is limited to those having a short chain of 10 or less, so that the hydrophobicity of the colloidal silica becomes insufficient, and the amount of the colloidal silica compounded If it exceeds 15 weight percent, it will gel and a sufficient amount of silica cannot be added, so a reduction in linear expansion coefficient cannot be expected.
• Patent Document 5 discloses a composite composition obtained by removing an organic solvent of a composition having a specific alicyclic structure and containing a bifunctional (meth) acrylate and colloidal silica dispersed in an organic solvent, A cured product obtained by crosslinking is disclosed.
• the dispersibility of silica in the composite composition and the suppression of curing shrinkage are insufficient.
• a silane compound having an alicyclic structure is added to the composition in order to supplement the dispersibility of silica and to reduce the viscosity of the composite composition. Very slow. For this reason, there is a problem that it is not economical in terms of manufacturing time and the effect is difficult to be exhibited.
• patent document 5 has description regarding a linear expansion coefficient, hardening shrinkage
• the object of the present invention is to solve the problems associated with the prior art. That is, according to the present invention, one or more properties among the transparency and heat resistance of the cured product formed, the storage stability of the composition, the handling property, and the moldability are improved as compared with the conventional curable composition. An object is to provide a curable composition.
• the present invention relates to the following [1] to [13], for example.
• A Silica fine particles surface-modified with one or more silane compounds containing at least a polymerizable silane compound (A1) represented by the following general formula (1), (B) (meth) acrylate compound, And (C) a curable composition containing a polymerization initiator:
• R 1 is a hydrocarbon group having 11 to 20 carbon atoms having an ethylenically unsaturated group, or a carbon group having an ethylenically unsaturated group and having an ether bond and / or an ester bond.
• R 2 represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms
• R 3 represents a halogen atom
• R 4 represents a hydrogen atom or a hydrocarbon having 1 to 10 carbon atoms Represents a group.
• a is an integer of 1 to 3
• b is an integer of 0 to 2
• c is an integer of 0 to 3
• the sum of a and b is 1 to 3
• the sum of a, b, and c is 1 to 4.
• a is 2 or more
• a plurality of R 1 may be the same or different
• b is 2
• a plurality of R 2 may be the same or different
• c is 2
• a plurality of R 3 may be the same or different from each other
• a plurality of R 4 may be the same or different when the sum of a, b and c is 1 or 2.
• the (meth) acrylate compound (B) has one or more (meth) acryloyloxy groups and no (meth) acrylate compound (B1) having a ring structure, and 1 (meth) acryloyloxy group.
• R 2 to R 4 have the same meanings as in the formula (1), R 5 represents a hydrogen atom or a methyl group, d is an integer of 8 to 16, Is an integer from 0 to 2, f is an integer from 0 to 3, and the sum of e and f is from 0 to 3.
• e 2
• f 2 or more
• a plurality of R 3 may be the same or different from each other
• e and f When R is 0 or 1, a plurality of R 4 may be the same as or different from each other.
• the silica fine particles (A) are silica fine particles whose surfaces are modified with a silane compound containing the polymerizable silane compound (A1) and a silane compound (A2) other than the polymerizable silane compound (A1).
• the curable composition according to any one of [1] to [3].
• the silane compound used for the surface modification does not include a polymerizable silane compound (A2 ′) represented by the following general formula (2 ′).
• silica fine particles (A) are silica fine particles whose surface is modified with 5 to 100 parts by mass of the silane compound with respect to 100 parts by mass of the silica fine particles before surface modification.
• one or more properties among the transparency and heat resistance of the formed cured product, the storage stability of the composition, the handling property and the moldability are improved as compared with the conventional curable composition.
• a cured product having a high light transmittance and a low linear expansion coefficient can be provided, and it does not gel during preparation and storage, and has a low viscosity. Further, it is possible to provide a curable composition having a small shrinkage ratio upon curing.
• a curable composition of the present invention a cured product obtained by curing the composition (hereinafter also simply referred to as “cured product”), a method for producing the same, and an optical material / electronic material comprising the cured product.
• cured product a cured product obtained by curing the composition
• an optical material / electronic material comprising the cured product.
• the curable composition of the present invention comprises (A) silica fine particles surface-modified with one or more silane compounds including at least the polymerizable silane compound (A1) represented by the general formula (1), and (B) ( A (meth) acrylate compound and (C) a polymerization initiator are contained.
• these components are also referred to as “component (A)”, “component (B)”, and “component (C)”, and the silica fine particles (A) surface-modified with the silane compound are referred to as “surface-modified silica fine particles”.
• polymerizability” of the polymerizable silane compound indicates polymerization based on a carbon-carbon double bond reaction.
• silica fine particles dispersed in an organic solvent when silica fine particles dispersed in an organic solvent are used as the silica fine particles to be surface-modified, “100 parts by mass of silica fine particles before surface modification” means “dispersed in an organic solvent” unless otherwise specified. "Mass of silica fine particles only” (that is, does not include the mass of organic solvent).
• (meth) acrylate compound means an acrylate compound and / or a methacrylate compound.
• the “(meth) acryloyloxy group” means an acryloyloxy group and / or a methacryloyloxy group.
• the curable composition of the present invention contains silica fine particles (A) surface-modified with a specific silane compound, the viscosity in the state of the composition is low and the handling property is excellent.
• the polymerizable silane compound (A1) (chemical structure is changed) bonded to the silica fine particles by surface modification is a (meth) acrylate compound (B) (preferably a (meth) acrylate compound (B1) described later or By reacting with the (meth) acrylate compound (B2)), the dispersion stability of the silica fine particles (A) in the curable composition is improved.
• the (meth) acrylate compound (B) and the silica fine particles (A) surface-modified with a specific silane compound are used together with the polymerization initiator (C), whereby the curable composition of the present invention is Hardened by the polymerization reaction, resulting in a cured product that has excellent heat resistance (low linear expansion coefficient as an index) and transparency equal to or higher than that of conventional products (high light transmittance as an index) .
• the presence of the silica fine particles (A) surface-modified with a specific silane compound suppresses the curing shrinkage of the composition, resulting in a cured product (which is formed as a cured film on the substrate). In addition, the warpage of the cured product becomes brittle or cracks can be prevented.
• the silica fine particles (A) are surface-modified silica fine particles obtained by surface-modifying silica fine particles with at least one silane compound containing at least a polymerizable silane compound (A1).
• silica fine particles surface-modified with silane compound As silica fine particles whose surface is modified with a silane compound, conventionally known silica fine particles can be used. Alternatively, porous silica sol, or a composite metal oxide of aluminum, magnesium, zinc, or the like and silicon may be used.
• the silica fine particles are not particularly limited in particle size, but it is preferable to use particles having an average particle size of 1 to 1000 nm. From the viewpoint of the transparency of the cured product, the average particle size is more preferably 1 to 500 nm, and most preferably 1 to 100 nm. Further, in order to increase the filling amount of the silica fine particles into the cured product of the present invention, silica fine particles having different average particle diameters may be mixed and used.
• the average particle size of the silica fine particles (before surface modification) was determined by observing the silica fine particles with a high-resolution transmission electron microscope (H-9000 type, manufactured by Hitachi, Ltd.) and arbitrarily measuring 100 particles from the observed fine particle image. This is a value obtained by selecting a silica particle image and obtaining the number average particle diameter by a known image data statistical processing technique.
• the preferred range of the average particle size of the silica fine particles (before surface modification) is usually also the preferred range of the average particle size of the silica fine particles (A) (after surface modification).
• the silica fine particles (A) are surface-modified silica fine particles obtained by surface-modifying silica fine particles with at least one silane compound containing at least a polymerizable silane compound (A1).
• the polymerizable silane compound (A1) is used for improving the dispersion stability of the silica fine particles in the curable composition.
• the dispersion stability of the silica fine particles can be improved.
• the viscosity of the curable composition is remarkably increased and gelation is not preferable.
• silane compound at least a polymerizable silane compound (A1) is used, and from the viewpoint of reducing the shrinkage when the curable composition is cured, a silane compound (A2) described later in addition to the polymerizable silane compound (A1). ) Can be used.
• the polymerizable silane compound (A1) is represented by the general formula (1).
• R 1 represents a hydrocarbon group having 11 to 20 carbon atoms having an ethylenically unsaturated group or a substituted hydrocarbon group having 11 to 20 carbon atoms.
• the substituted hydrocarbon group has an ethylenically unsaturated group and has an ether bond and / or an ester bond.
• the substituted hydrocarbon group include a (meth) acryloyloxyalkyl group.
• the substituted hydrocarbon group has an ester bond and an ethylenically unsaturated group, it means the total number of carbon atoms including the ester bond and the ethylenically unsaturated group.
• R 1 is preferably a substituted hydrocarbon group having 11 to 20 carbon atoms having an ethylenically unsaturated group, and more preferably a substituted hydrocarbon group having 11 to 20 carbon atoms having a (meth) acryloyloxy group.
• the polymerizable silane compound (A1) having a specific long-chain carbon chain (R 1 ) is used for the surface modification of the silica fine particles, so that the viscosity of the curable composition can be reduced.
• the surface modification of silica fine particles, R 1 is 10 or less carbon atoms (substituted) silane compound hydrocarbon group (e.g., 3-methacryloyloxy propyl trimethoxy silane) is used alone, significantly the viscosity of the curable composition It is not preferable because it increases and gels.
• R 2 represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms (eg, alkyl group).
• R 3 represents a halogen atom (eg, fluorine atom, chlorine atom, bromine atom).
• R 4 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (eg, alkyl group).
• a is an integer from 1 to 3, preferably 1; b is an integer from 0 to 2, preferably 0; c is an integer from 0 to 3, preferably 0; The sum of b is 1 to 3; the sum of a, b and c is 1 to 4, preferably an integer of 1 to 3.
• a plurality of R 1 may be the same or different, and when b is 2, a plurality of R 2 may be the same or different, and c is 2
• a plurality of R 3 may be the same or different from each other, and a plurality of R 4 may be the same or different when the sum of a, b and c is 1 or 2.
• polymerizable silane compound (A1) from the viewpoint of transparency of the curable composition of the present invention, a polymerizable silane compound (A1 ′) represented by the general formula (1 ′) ((meth) acryloyloxy group) is used. Having a silane compound).
• R 2 represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms (eg, an alkyl group), and is preferably a methyl group or an ethyl group from the viewpoint of storage stability and handling properties of the silane compound.
• a methyl group is particularly preferred because of its ease of synthesis.
• R 3 represents a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), and is preferably a chlorine atom from the viewpoint of storage stability and handling properties of the silane compound.
• a halogen atom eg, fluorine atom, chlorine atom, bromine atom
• R 4 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (eg, alkyl group). From the viewpoint of storage stability and handling properties of the silane compound and ease of synthesis of the silane compound, R 4 represents a methyl group. Or it is preferable that it is an ethyl group.
• R 5 represents a hydrogen atom or a methyl group.
• d is an integer of 8 to 16, preferably an integer of 8 to 10; e is an integer of 0 to 2, preferably 0; f is an integer of 0 to 3, preferably 0. Yes; the sum of e and f is 0-3, preferably an integer of 0-2.
• d is an integer of 8 to 10
• e is an integer of 0 to 2
• f is preferably
• d is an integer of 8 to 10
• e is 0.
• f is particularly preferably 0.
• a plurality of R 2 may be the same or different from each other, and when f is 2 or more, a plurality of R 3 may be the same or different from each other, e and f When R is 0 or 1, a plurality of R 4 may be the same as or different from each other.
• Examples of the polymerizable silane compounds (A1) and (A1 ′) include 8-acryloyloxyoctyldimethylmethoxysilane, 8-acryloyloxyoctylmethyldimethoxysilane, 8-acryloyloxyoctyldiethylmethoxysilane, and 8-acryloyloxyoctylethyl.
• Dimethoxysilane 8-acryloyloxyoctyltrimethoxysilane, 8-acryloyloxyoctyldimethylethoxysilane, 8-acryloyloxyoctylmethyldiethoxysilane, 8-acryloyloxyoctyldiethylethoxysilane, 8-acryloyloxyoctylethyldiethoxysilane, 8-acryloyloxyoctyltriethoxysilane, 8-methacryloyloxyoctyldimethylmethoxysilane, 8-methacryloylo Siooctylmethyldimethoxysilane, 8-methacryloyloxyoctyldiethylmethoxysilane, 8-methacryloyloxyoctylethyldimethoxysilane, 8-methacryloyloxyoctylethyldimethoxys
• 8-methacryloyloxyoctyltrimethoxysilane and 8-methacryloyloxyoctyltriethoxysilane are preferable from the viewpoint of reducing the viscosity and improving the storage stability of the curable composition of the present invention.
• the polymerizable silane compound (A1) may be used alone or in combination of two or more.
• the polymerizable silane compound (A1) can be produced by a known method and is also commercially available.
• silane compound (A2) In the present invention, if necessary (for example, from the viewpoint of reducing the shrinkage rate when the curable composition is cured), in addition to the polymerizable silane compound (A1) (other than the polymerizable silane compound (A1)) One or more silane compounds (A2) can be used.
• the silane compound (A2) is not particularly limited.
• silane compounds having a group or the like include silane compounds having a group or the like.
• silane compound (A2) examples include tetraethoxysilane, tetramethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, trimethylchlorosilane, phenyltrimethoxysilane, phenylmethyldimethoxysilane, diphenyldimethoxy.
• the polymerizable silane compound (A2 ′) represented by the following general formula (2 ′) may not be used as the silane compound (A2). .
• R 2 to R 5 and e and f have the same meanings as those in the formula (1 ′), and when R 5 is a hydrogen atom, g is an integer of 1 to 7, When R 5 is a methyl group, g is an integer of 1 to 6.
• silane compound (A2) among the above-mentioned compounds, dimethyldimethoxysilane, trimethylmethoxysilane, trimethylchlorosilane, phenyltrimethoxysilane, phenylmethyldimethoxysilane, diphenyldimethoxysilane, trifluoropropyltrimethyl from the viewpoint of heat resistance of the cured product.
• Methoxysilane and trifluoropropyltriethoxysilane are preferred.
• the silane compound (A2) may be used alone or in combination of two or more, and the number of types is not particularly limited, but from the viewpoint of simplification during synthesis, preferably 1 to 2 types, One type is preferred.
• silica fine particles (A) surface-modified silica fine particles
• the silica fine particles are surface-modified with one or more silane compounds including at least a polymerizable silane compound (A1).
• the detailed conditions of the surface modification are as described in the column of “Step 1” in ⁇ Method for producing curable composition> described later.
• the total amount of the silane compound used for the surface modification (eg, when the silane compound (A2) is used, in addition to the amount of the polymerizable silane compound (A1), the amount of the silane compound (A2) is included)
• the amount is usually 5 to 100 parts by weight, preferably 20 to 50 parts by weight, and most preferably 25 to 35 parts by weight with respect to 100 parts by weight of the silica fine particles (this is the amount of silica alone containing no solvent).
• the amount of the silane compound used is less than the above range, the viscosity of the composition increases, and the dispersibility of the silica fine particles (A) in the composition deteriorates to cause gelation or the cured product obtained from the composition.
• the heat resistance may decrease. If the amount of the silane compound used exceeds the above range, a reaction between the silica fine particles may occur during surface modification of the silica fine particles, thereby causing aggregation or gelation of the silica fine particles (A) in the composition.
• the amount of the polymerizable silane compound (A1) is usually 1 to 100% by mass, preferably 10 to 100% by mass, and more preferably 20 to 100% by mass with respect to the total amount of the silane compound used for the surface modification.
• the amount of the polymerizable silane compound (A2 ′) with respect to the total amount of the silane compound used for the surface modification is preferably 5% by mass or less, more preferably from the viewpoint of preventing increase in viscosity and gelation of the curable composition. Is 0% by mass.
• Silica fine particles (A) in the curable composition of the present invention are 100 parts by mass of the total amount of silica fine particles (A) in terms of silica fine particles before surface modification and the amount of (meth) acrylate compound (B).
• the silica fine particle (A) is preferably blended so that the amount of the silica fine particle before surface modification is 1 to 90 parts by mass, more preferably 15 to 65 parts by mass, and 45 to 55 parts by mass. Most preferably.
• the amount of the silica fine particles (A) in terms of “silica fine particles before surface modification” is, for example, z parts by mass of silica fine particles obtained by surface-modifying x parts by mass of silica fine particles with y parts by mass of a silane compound. In the case of the curable composition containing (A), the amount is calculated based on x parts by mass of silica fine particles.
• the content of the silica fine particles (A) is within the above range, the fluidity of the composition and the dispersibility of the silica fine particles (A) in the composition are good. Therefore, if the said composition is used, the hardened
• the (meth) acrylate compound (B) has a (meth) acryloyloxy group.
• Examples of the (meth) acrylate compound (B) include one or more (meth) acrylate compounds (B1) having one or more (meth) acryloyloxy groups and no ring structure, and one or more (meth) acryloyloxy groups. And a (meth) acrylate compound (B2) having an alicyclic structure.
• these are also simply referred to as (meth) acrylate (B1) and (meth) acrylate (B2).
• the curable composition of the present invention preferably contains at least either (meth) acrylate (B1) or (meth) acrylate (B2) as the (meth) acrylate compound (B). More preferably, both (B1) and (meth) acrylate (B2) are included.
• the (meth) acrylate compound (B) in the curable composition of the present invention is a total amount of the amount of the silica fine particle (A) in terms of silica fine particle before surface modification and the amount of the (meth) acrylate compound (B).
• the amount of the (meth) acrylate compound (B) is preferably 10 to 99 parts by mass with respect to 100 parts by mass, more preferably 35 to 85 parts by mass, and 45 to 55 parts by mass. Most preferably it is.
• the (meth) acrylate (B1) is a (meth) acrylate compound having at least one (meth) acryloyloxy group and having no ring structure.
• the number of (meth) acryloyloxy groups in (B1) is not particularly limited as long as it is 1 or more, but is preferably 2 or more, more preferably 2 to 6.
• Examples of (meth) acrylate (B1) include methoxypolyethylene glycol (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, polyethylene glycol di ( (Meth) acrylate, polypropylene glycol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, glycerin di (meth) Methacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) Acrylate, dipentaerythritol pent
• Method (Meth) acrylate (B1) may be used alone or in combination of two or more.
• the (meth) acrylate (B2) is a (meth) acrylate compound having one or more (meth) acryloyloxy groups and having an alicyclic structure.
• the alicyclic structure is a structure in which an aromatic ring structure is excluded from a structure in which carbon atoms are bonded in a ring shape.
• the number of (meth) acryloyloxy groups in the above (B2) is not particularly limited as long as it is 1 or more, but is preferably 1 to 5, more preferably 1 to 3.
• the alicyclic structure of (B2) is not particularly limited, but preferably a cyclopentane structure, a cyclohexane structure, a cyclodecane structure, an isobornyl structure, an adamantane structure, a combination of these structures, or two of these structures as a basic skeleton.
• One having one or more structures to which a double bond is added more preferably a cyclohexane structure, a cyclopentane structure, a dicyclopentane structure, a cyclodecane structure, a tricyclodecane structure, an adamantane structure, or a double bond added to these structures Those having one or more structures, more preferably those having one or more tricyclodecane structures or adamantane structures.
• (meth) acrylate (B2) for example, Cyclohexanedimethanol mono (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, bornyl (meth) acrylate Monofunctional (meth) acrylates such as isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, tricyclodecane dimethanol mono (meth) acrylate, adamantyl (meth) acrylate; Cyclohexanedimethanol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, dicyclopentenyl di (meth) acrylate, dicyclopentadienyl di (meth) acrylate, bornyl di (meth) acrylate, is
• monofunctional (meth) acrylate is preferable, and dicyclopentadienyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and adamantyl (meth) acrylate are more preferable from the viewpoint of transparency and heat resistance of the cured product. preferable.
• Method (Meth) acrylate (B2) may be used alone or in combination of two or more.
• the (meth) acrylate compound (B) may contain only one of (B1) and (B2), but preferably contains both (B1) and (B2).
• Polymerization initiator (C) examples include a photopolymerization initiator that generates radicals and a thermal polymerization initiator. These compounds contribute to the curability of the curable composition of the present invention.
• photopolymerization initiator examples include benzophenone, benzoin methyl ether, benzoin propyl ether, diethoxyacetophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethyl.
• photoinitiators may be used independently and may use 2 or more types together.
• the content of the photopolymerization initiator in the curable composition of the present invention may be an amount that allows the composition to be appropriately cured, and is usually 0.1% relative to 100 parts by mass of the composition excluding the photopolymerization initiator.
• the amount is from 01 to 15 parts by mass, preferably from 0.02 to 10 parts by mass, and more preferably from 0.1 to 5 parts by mass. If the content of the photopolymerization initiator is too large, the storage stability of the composition will be lowered, colored, or problems such as cracking during curing due to rapid progress of crosslinking when obtaining a cured product by crosslinking. May occur. Moreover, when there is too little content of a photoinitiator, a composition may not fully be hardened
• thermal polymerization initiator examples include benzoyl peroxide, diisopropyl peroxycarbonate, t-butyl peroxy (2-ethylhexanoate), t-butyl peroxyneodecanoate, t-hexyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropylmonocarbo Nate, dilauroyl peroxide, diisopropyl peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, 2,2-di (4,4-di- (t-butylperoxy) cyclohexyl) propane Can be mentioned. These thermal polymerization initiators may be used alone or in combination of two or more.
• the content of the thermal polymerization initiator in the curable composition of the present invention may be an amount that allows the composition to be appropriately cured, and is usually 0.1 parts by mass with respect to 100 parts by mass of the composition excluding the thermal polymerization initiator.
• the amount is from 01 to 15 parts by mass, preferably from 0.02 to 10 parts by mass, and more preferably from 0.1 to 5 parts by mass. If the content of the thermal polymerization initiator is too large, the storage stability of the composition will be reduced, colored, or problems such as cracking during curing due to rapid progress of crosslinking when obtaining a cured product by crosslinking. May occur. Moreover, when there is too little content of a thermal-polymerization initiator, a composition may not fully be hardened
• the curable composition of the present invention can be used as long as the viscosity of the composition and the properties of the cured product, such as transparency and heat resistance, are not impaired.
• the curable composition of this invention does not contain an organic solvent and water substantially.
• substantially means that when a cured product is actually obtained using the curable composition of the present invention, it is not necessary to go through a step of removing the solvent again, specifically, the curable composition. It means that the remaining amount of each of the organic solvent and water in the product is preferably 1% by mass or less, more preferably 0.5% by mass or less.
• the polymerization inhibitor can be used to prevent components contained in the curable composition from causing a polymerization reaction during storage.
• examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, benzoquinone, pt-butylcatechol, and 2,6-di-t-butyl-4-methylphenol.
• the content of the polymerization inhibitor is preferably 0.1 parts by mass or less with respect to 100 parts by mass of the curable composition excluding the polymerization inhibitor.
• a polymerization inhibitor may be used independently and may use 2 or more types together.
• Leveling agent examples include polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, polyether-modified methylalkylpolysiloxane copolymer, aralkyl-modified methylalkylpolysiloxane copolymer, and polyether-modified.
• a methyl alkyl polysiloxane copolymer is mentioned.
• a leveling agent may be used independently and may use 2 or more types together.
• the antioxidant is a compound having a function of capturing an oxidation promoting factor such as a free radical.
• the antioxidant is not particularly limited as long as it is an antioxidant generally used industrially, and examples thereof include a phenol-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant.
• phenolic antioxidants examples include Irganox 1010 (IRGANOX 1010: pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by BASF Japan Ltd.), Irga Knox 1076 (IRGANOX 1076: octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, manufactured by BASF Japan Ltd.), Irganox 1330 (IRGANOX 1330: 3, 3 ′, 3 ′ ', 5,5', 5 ′′ -hexa-t-butyl-a, a ′, a ′′-(mesitylene-2,4,6-triyl) tri-p-cresol, manufactured by BASF Japan Ltd.) Irganox 3114 (IRGANOX 3114: 1,3,5-Tris (3, -Di-t-butyl-4-hydroxybenzyl)
• Examples of phosphorus antioxidants include Irgaphos 168 (IRGAFOS 168: Tris (2,4-di-t-butylphenyl) phosphite, manufactured by BASF Japan Ltd.), Irgaphos 12 (IRGAFOS 12: Tris [2- [[2,4,8,10-tetra-t-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] ethyl] amine, manufactured by BASF Japan Ltd.) Irgaphos 38 (IRGAFOS 38: bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl) ethyl ester phosphorous acid, manufactured by BASF Japan), Adeka Stub 329K (manufactured by ADEKA) ), ADK STAB PEP36 (manufactured by ADEKA), ADK STAB PEP-8 (manufactured by ADEKA), and
• sulfur-based antioxidant examples include dialkylthiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl or distearyl, and ⁇ -alkyl mercaptopropionic acids of polyols such as tetrakis [methylene (3-dodecylthio) propionate] methane An ester compound is mentioned.
• the content of the antioxidant is 0.1 to 10 parts by mass with respect to 100 parts by mass of the curable composition excluding the antioxidant, since it may be colored or hindered when added in a large amount. It is preferable.
• An antioxidant may be used independently and may use 2 or more types together.
• the ultraviolet absorber is a compound that can absorb ultraviolet rays having a wavelength of about 200 to 380 nm and change the energy into energy such as heat and infrared rays to be released.
• the ultraviolet absorber is not particularly limited as long as it is generally used industrially.
• benzotriazole type triazine type, diphenylmethane type, 2-cyanopropenoic acid ester type, salicylic acid ester type, anthranilate type Cinnamic acid derivative-based, camphor derivative-based, resorcinol-based, oxalinide-based, coumarin derivative-based UV absorbers, and the like can be used in the present invention.
• An ultraviolet absorber may be used independently and may use 2 or more types together.
• benzotriazole-based UV absorber examples include 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6 [(2H-benzotriazol-2-yl) phenol]], 2 -(2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl -6- (t-butyl) phenol is mentioned.
• triazine ultraviolet absorber examples include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2,4,6-tris. -(Diisobutyl 4'-amino-benzalmalonate) -s-triazine, 4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy- 4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4- Dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2 Hydroxy-4-dodec
• diphenylmethane ultraviolet absorber examples include diphenylmethanone, methyldiphenylmethanone, 4-hydroxydiphenylmethanone, 4-methoxydiphenylmethanone, 4-octoxydiphenylmethanone, 4-decyloxydiphenylmethanone, 4 -Dodecyloxydiphenylmethanone, 4-benzyloxydiphenylmethanone, 4,2 ', 4'-trihydroxydiphenylmethanone, 2'-hydroxy-4,4'-dimethoxydiphenylmethanone, 4- (2-ethylhexyl) Oxy) -2-hydroxy-diphenylmethanone, methyl o-benzoylbenzoate, benzoin ethyl ether.
• 2-cyanopropenoic acid ester ultraviolet absorbers examples include ethyl ⁇ -cyano- ⁇ , ⁇ -diphenylpropenoic acid ester and isooctyl ⁇ -cyano- ⁇ , ⁇ -diphenylpropenoic acid ester.
• Examples of the salicylic acid ester UV absorber include isocetyl salicylate, octyl salicylate, glycol salicylate, and phenyl salicylate.
• Examples of the anthranilate-based ultraviolet absorber include menthyl anthranilate.
• Cinnamic acid derivative-based ultraviolet absorbers include, for example, ethylhexylmethoxycinnamate, isopropylmethoxycinnamate, isoamylmethoxycinnamate, diisopropylmethylcinnamate, glyceryl-ethylhexanoate dimethoxycinnamate, methyl- ⁇ -carbomethoxycinnamate Methyl- ⁇ -cyano- ⁇ -methyl-p-methoxycinnamate.
• camphor derivative-based ultraviolet absorber examples include benzylidene camphor, benzylidene camphor sulfonic acid, camphor benzalkonium methosulfate, terephthalidene dicamphor sulfonic acid, and polyacrylamide methylbenzylidene camphor.
• resorcinol-based ultraviolet absorber examples include dibenzoyl resorcinol bis (4-t-butylbenzoyl resorcinol).
• Examples of the oxalinide-based ultraviolet absorber include 4,4′-di-octyloxy oxanilide, 2,2′-diethoxyoxy oxanilide, and 2,2′-di-octyloxy-5,5′-.
• Examples of the coumarin derivative ultraviolet absorber include 7-hydroxycoumarin.
• a metal complex compound can be used, and specific examples include a phthalocyanine compound, a naphthalocyanine compound, and a dithiol metal complex compound.
• the light stabilizer is a compound having an effect of reducing auto-oxidative decomposition due to radicals generated by light energy and suppressing deterioration of a cured product.
• the light stabilizer is not particularly limited as long as it is generally used industrially, and examples thereof include hindered amine compounds (hereinafter also referred to as “HALS”), benzophenone compounds, and benzotriazole compounds.
• HALS hindered amine compounds
• benzophenone compounds benzophenone compounds
• benzotriazole compounds benzotriazole compounds
• the compound which has a (meth) acryloyloxy group is also contained in a light stabilizer.
• Some of the light stabilizers having a (meth) acryloyloxy group correspond to the (meth) acrylate compound (B), and they are (meth) acrylate compounds (B) and at the same time a light stabilizer. I reckon.
• HALS includes, for example, N, N ′, N ′′, N ′ ′′-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidine-4 -Yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine and 1,3,5-triazine and N, N'-bis (2,2,6,6) -Polycondensate with tetramethyl-4-piperidyl) butylamine, poly [ ⁇ (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl ⁇ ⁇ (2 , 2,6,6-tetramethyl-4-piperidyl) imino ⁇ hexamethylene ⁇ (2,2,6,6-tetramethyl-4-piperidyl) imino ⁇ ], 1,6-hexanediamine-N, N ′ -Bis
• High molecular weight HALS polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 1,2,3,4-butanetetracarboxylic acid and 1,2,2 , 6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane It includes pentamethyl piperidinylmethyl methacrylate; such ester, piperidine ring linked to a high molecular weight HALS via an ester bond.
• the content of the light stabilizer is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the curable composition excluding the light stabilizer from the viewpoint of colorability.
• a light stabilizer may be used independently and may use 2 or more types together.
• Filler, Pigment examples include calcium carbonate, talc, mica, clay, aluminosilicate, Aerosil (registered trademark), graphite, carbon nanotube, barium sulfate, aluminum hydroxide, zirconium oxide, zinc stearate, zinc white, Examples include Bengala and azo pigments.
• the viscosity of the curable composition of the present invention at 25 ° C. measured with a B-type viscometer DV-III ULTRA is usually 50 to 20,000 mPa ⁇ s, preferably 100 to 8,000 mPa ⁇ s. It is.
• the curable composition of the present invention has an appropriate viscosity even when it does not contain a solvent, and has good handling properties. This is because the silica fine particles (A) based on the surface modification of the silica fine particles described above have high reactivity and compatibility with the (meth) acrylate compound (B), and high dispersion stability in the (meth) acrylate compound (B). caused by.
• the curable composition of the present invention includes, for example, a step of obtaining silica fine particles (A) by surface-modifying silica fine particles with the above silane compound (step 1); silica fine particles (A) obtained in step 1; A step of mixing the (meth) acrylate compound (B) and other components as necessary to obtain a mixed solution (step 2); volatile components are distilled off from the mixed solution obtained in step 2 (hereinafter referred to as “ (Also referred to as “desolvation”) to obtain a mixture (step 3); add and mix the polymerization initiator (C) and, if necessary, other components to the mixture obtained in step 3, It can manufacture by performing the process (process 4) of obtaining a curable composition one by one.
• step 1 the surface of the silica fine particles is modified with one or more silane compounds including at least a polymerizable silane compound (A1).
• A1 a polymerizable silane compound
• hydrolysis / condensation polymerization of the silane compound proceeds on the surface of the silica fine particles.
• silica fine particles it is preferable to use a dispersion (colloidal silica) in which silica fine particles are dispersed in an organic solvent from the viewpoint of dispersibility in the curable composition.
• organic solvent it is preferable to use what melt
• the content of the silica fine particles in the dispersion is usually 1 to 60% by mass, preferably 10 to 50% by mass, and more preferably 20 to 40% by mass from the viewpoint of dispersibility in the curable composition.
• organic solvent examples include alcohol solvents, ketone solvents, ester solvents, and glycol ether solvents.
• organic solvents such as alcohol solvents such as methanol, ethanol, isopropyl alcohol, butyl alcohol and n-propyl alcohol; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone;
• the dispersion can be produced by a conventionally known method and is commercially available.
• Other silica fine particles described above can also be produced by a conventionally known method, and are also commercially available.
• silica fine particles preferably colloidal silica
• one or more silane compounds including at least the polymerizable silane compound (A1) are added while stirring, and the mixture is stirred and mixed.
• Water and a catalyst necessary for hydrolyzing the compound are added, and the silane compound is hydrolyzed while being stirred and subjected to condensation polymerization on the surface of the silica fine particles.
• the amount of the silane compound used to modify the surface of the silica fine particles (for example, when using the silane compound (A2), the amount of the polymerizable silane compound (A1)
• the amount of the silane compound (A2) is usually 5 to 100 parts by weight, preferably 20 to 50 parts by weight, most preferably 25 to 35 parts by weight based on 100 parts by weight of the silica fine particles before surface modification. Part.
• the amount of water required for the hydrolysis is usually 0.1 to 10 mole equivalent, preferably 1 to 10 mole equivalent, more preferably 1 to 5 mole relative to 1 mole equivalent of the silane compound. Is equal. If the amount of water is too small, the hydrolysis rate may become extremely slow, resulting in poor economic efficiency, and insufficient surface modification. If the amount of water is excessively large, the silica fine particles (A) may form a gel.
• a catalyst for the hydrolysis reaction is usually used.
• Examples of the catalyst for the hydrolysis reaction include inorganic acids such as hydrochloric acid (aqueous hydrogen chloride), acetic acid, sulfuric acid and phosphoric acid; formic acid, propionic acid, oxalic acid, paratoluenesulfonic acid, benzoic acid, phthalic acid and maleic acid
• Organic acids such as potassium hydroxide, sodium hydroxide, calcium hydroxide and ammonia; organic metals; metal alkoxides; organotin compounds such as dibutyltin dilaurate, dibutyltin dioctylate and dibutyltin diacetate; aluminum tris (acetyl) Acetonate), titanium tetrakis (acetylacetonate), titanium bis (butoxy) bis (acetylacetonate), titanium bis (isopropoxy) bis (acetylacetonate), zirconium bis (butoxy) bis (acetylacetate) Sulfonate) and zirconium
• the catalyst for the hydrolysis reaction may be used alone or in combination of two or more.
• a water-insoluble catalyst when one or more silane compounds are hydrolyzed, a water-insoluble catalyst may be used, but a water-soluble catalyst is preferably used.
• a water-soluble catalyst for hydrolysis reaction it is preferable to dissolve the water-soluble catalyst in an appropriate amount of water and add it to the reaction system because the catalyst can be uniformly dispersed.
• the amount of the catalyst used for hydrolysis is not particularly limited.
• the catalyst may be used in the hydrolysis reaction as an aqueous solution dissolved in water. In that case, the amount of the catalyst added is only the catalyst (for example, acid or base) contained in the aqueous solution. Represents an amount.
• the reaction temperature of the hydrolysis reaction is not particularly limited, but is usually in the range of 10 to 80 ° C, preferably in the range of 20 to 50 ° C. If the reaction temperature is excessively low, the hydrolysis rate may be extremely slow, resulting in lack of economic efficiency and insufficient surface modification. When the reaction temperature is excessively high, the gelation reaction tends to occur.
• the reaction time for conducting the hydrolysis reaction is not particularly limited, but is usually in the range of 10 minutes to 48 hours, preferably 30 minutes to 24 hours.
• the surface modification with two or more silane compounds in Step 1 may be performed sequentially for each silane compound, but it is preferable to perform the surface modification at the same time in terms of simplification and efficiency of the reaction process.
• Step 2 there is no particular limitation on the method of mixing the silica fine particles (A) obtained in the step 1, the (meth) acrylate compound (B), and other components as necessary.
• a mixer such as a mixer, a ball mill, or a three-roller at room temperature or under heating conditions
• step 3 in order to distill off (desolvent) volatile components such as organic solvent and water from a mixed solution of silica fine particles (A) and (meth) acrylate compound (B), the mixed solution is used in a reduced pressure state. Is preferably heated.
• the temperature is preferably maintained at 20 to 100 ° C., more preferably 30 to 70 ° C., and further preferably 30 to 50 ° C. in terms of the balance between aggregation gelation prevention and desolvation speed. If the temperature is raised too much, the fluidity of the curable composition may be extremely lowered or become a gel.
• the degree of vacuum at the time of depressurization is usually 10 to 4,000 kPa, more preferably 10 to 1,000 kPa, and most preferably 10 to 500 kPa, in order to balance the solvent removal speed and prevention of aggregation gelation. . If the value of the degree of vacuum is too large, the solvent removal speed becomes extremely slow and the economy may be lacking.
• the mixture after desolvation contains substantially no organic solvent and water.
• substantially means that when a cured product is actually obtained using the curable composition of the present invention, it is not necessary to go through a step of removing the solvent again, specifically, the curable composition. It means that the remaining amount of each of the organic solvent and water in the product is preferably 1% by mass or less, more preferably 0.5% by mass or less.
• a polymerization inhibitor may be added so that the addition amount is 0.1 parts by mass or less with respect to 100 parts by mass of the mixture after the solvent removal.
• the polymerization inhibitor can be used to prevent the contained component from causing a polymerization reaction during the solvent removal process or during storage of the curable composition after the solvent removal.
• step 3 the mixed liquid of silica fine particles (A) and (meth) acrylate compound (B) obtained in step 2 can be transferred to a dedicated apparatus, and step 2 is performed in step 1. If it was performed using the reactor which was made, it can also carry out in the said reactor following the process 2.
• FIG. 1 the mixed liquid of silica fine particles (A) and (meth) acrylate compound (B) obtained in step 2 can be transferred to a dedicated apparatus, and step 2 is performed in step 1. If it was performed using the reactor which was made, it can also carry out in the said reactor following the process 2.
• step 4 there is no particular limitation on the method of adding and mixing the polymerization initiator (C) and other components as necessary to the mixture after removing the solvent in step 3, for example, a mixer at room temperature, A method of mixing each of the above components by a mixer such as a ball mill or a three roll, the polymerization initiator (C) with continuous stirring in the reactor in which Steps 1 to 3 were performed, and other components as necessary And a method of adding and mixing them.
• the curable composition obtained by adding and mixing such a polymerization initiator (C) may be filtered as necessary. This filtration is performed for the purpose of removing foreign substances such as dust in the curable composition.
• the filtration method is not particularly limited, but a method of pressure filtration using a membrane type or cartridge type filter having a pressure filtration pore size of 1.0 ⁇ m is preferable.
• the curable composition of the present invention is obtained.
• a cured product is obtained by curing the curable composition of the present invention.
• the silica fine particles (A) and (meth) acrylate compounds (B) whose surfaces are modified with at least one silane compound containing the polymerizable silane compound (A1) are hardened. It has excellent heat resistance (low linear expansion coefficient as an index), and transparency equal to or higher than that of conventional products (high light transmittance as an index). Therefore, the cured product can be suitably used as an optical material / electronic material as described later.
• the cured product of the present invention comprising a curable composition containing silica fine particles (A) surface-modified with a silane compound and containing a (meth) acrylate compound (B) is in the range of 35 ° C. to 250 ° C.
• the average linear expansion coefficient is preferably 10 ppm or more, more preferably 20 ppm or more. The details of the method of measuring the average linear expansion coefficient are as described in the examples.
• the shrinkage ratio during curing of the curable composition of the present invention is preferably 15% or less, more preferably 10% or less, and still more preferably 8% or less.
• the details of the definition / measurement method of the shrinkage rate are as described in the examples.
• cured material of this invention has the process of hardening the curable composition of this invention.
• Examples of the curing method include a method of crosslinking ethylenically unsaturated groups by irradiation with active energy rays, and a method of thermally polymerizing ethylenically unsaturated groups by applying heat, and these may be used in combination.
• a photopolymerization initiator is contained in the curable composition in Step 4 described above.
• a thermal polymerization initiator is contained in the curable composition.
• the cured product of the present invention is formed by applying the curable composition of the present invention on a substrate such as a glass plate, a plastic plate, a metal plate, or a silicon wafer to form a coating film, and then applying active energy rays to the coating film.
• a substrate such as a glass plate, a plastic plate, a metal plate, or a silicon wafer
• active energy rays can be obtained by irradiating or heating the coating film.
• both irradiation with active energy rays and heating may be performed.
• Examples of the application method of the curable composition include application by a bar coater, applicator, die coater, spin coater, spray coater, curtain coater, or roll coater, application by screen printing, and application by dipping. .
• the coating amount of the curable composition of the present invention on the substrate is not particularly limited and can be appropriately adjusted according to the purpose, and is a film of a coating film obtained after the curing treatment by irradiation with active energy rays and / or heating.
• the thickness is preferably 1 ⁇ m to 10 mm, more preferably 10 to 1000 ⁇ m.
• the active energy ray used for curing is preferably an electron beam or light in the ultraviolet to infrared wavelength range.
• the light source for example, an ultra-high pressure mercury light source or a metal halide light source can be used for ultraviolet rays, a metal halide light source or a halogen light source can be used for visible rays, and a halogen light source can be used for infrared rays. Can be used.
• the irradiation amount of the active energy ray is appropriately set according to the type of the light source, the film thickness of the coating film, etc., but the reaction rate of the (meth) acryloyloxy group of the (meth) acrylate compound (B) is preferably 80%. As mentioned above, it can set suitably so that it may become 90% or more more preferably.
• the reaction rate is calculated from the change in the absorption peak intensity of the (meth) acryloyloxy group before and after the reaction by infrared absorption spectrum.
• curing may be further advanced by heat treatment (annealing treatment).
• the heating temperature at that time is preferably in the range of 80 to 220 ° C., and the heating time is preferably in the range of 10 to 60 minutes.
• the heating temperature is preferably in the range of 80 to 200 ° C, more preferably in the range of 100 to 160 ° C. If the heating temperature is lower than the above range, it is necessary to lengthen the heating time, which tends to be less economical. If the heating temperature exceeds the above range, it takes energy costs and also takes heating and cooling time. Therefore, it tends to lack economic efficiency.
• the heating time is appropriately set according to the heating temperature, the film thickness of the coating film, etc., but the reaction rate of the (meth) acryloyloxy group of the (meth) acrylate compound (B) is preferably 80% or more, more preferably It can set suitably so that it may become 90% or more.
• the reaction rate is calculated from the change in the absorption peak intensity of the (meth) acryloyloxy group before and after the reaction by the infrared absorption spectrum.
• the cured product of the present invention includes a transparent plate, an optical lens, an optical disk substrate, a plastic substrate for a liquid crystal display element, a substrate for a color filter, a plastic substrate for an organic EL display element, a substrate for a solar cell, a touch panel, an optical element, an optical waveguide, and an LED. It can be suitably used as an optical material / electronic material such as a sealing material.
• silica fine particles to be surface-modified isopropyl alcohol-dispersed colloidal silica (silica fine particle content 30 mass%, average particle size 10 to 20 nm, trade name: Snowtech IPA-ST; manufactured by Nissan Chemical Industries, Ltd.) was used.
• isopropyl alcohol-dispersed colloidal silica (amount including solvent) is placed in a separable flask, and 9 g of 8-methacryloyloxyoctyltrimethoxysilane (MOS) as a silane compound (A1) (surface in colloidal silica).
• MOS 8-methacryloyloxyoctyltrimethoxysilane
• A1 silane compound
• hydrochloric acid having a concentration of 0.1825% by mass is added and stirred at 25 ° C. for 24 hours. Modification was performed to obtain a dispersion containing surface-modified silica fine particles.
• the disappearance of the silane compound (here, MOS) due to hydrolysis was confirmed by gas chromatography (model 6850; manufactured by Agilent). Using nonpolar column DB-1 (manufactured by J & W), temperature 50-300 ° C, heating rate 10 ° C / min, using He as carrier gas, flow rate 1.2cc / min, for flame ionization detector The internal standard method was used. The MOS disappeared 24 hours after the addition of the hydrochloric acid.
• TMPTA trimethylolpropane triacrylate
• ADMA adamantyl methacrylate
• B2 an antioxidant Irganox 1135
• IRGANOX 1135 benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl ester; manufactured by BASF Japan Ltd.
• Example 2 Example except that the silane compound was changed to a mixture of 18 parts of 8-methacryloyloxyoctyltrimethoxysilane (MOS) and 12 parts of phenyltrimethoxysilane (PhS) with respect to 100 parts of silica fine particles before surface modification.
• MOS 8-methacryloyloxyoctyltrimethoxysilane
• PhS phenyltrimethoxysilane
• Example 1 A curable composition (Example 1) was prepared in the same manner as in Example 1 except that the amount of (meth) acrylate compound (B) was changed as shown in Table 2 without using silica fine particles and a silane compound. Y-1) was obtained. In addition, since this comparative example was different from Example 1 and the solvent derived from the colloidal silica dispersion was not added to the composition, the step of distilling off the solvent was omitted.
• Example 2 silica fine particles surface-modified with a silane compound were not used, unmodified isopropyl alcohol-dispersed colloidal silica was used as it was, and the amount of each component used was changed as shown in Table 2. Was obtained in the same manner as in Example 1 to obtain a curable composition (Y-2).
• Examples 8 to 16, Comparative Examples 3 to 32 In the same manner as in Example 1 except that the types and addition amounts of the silica fine particles, the silane compound and the (meth) acrylate compound (B) were changed as shown in Tables 2 to 8, the curability was the same as in Example 1. Compositions (X-8) to (X-16) and (Y-3) to (Y-32) were obtained.
• the example in which the addition amount of the silica fine particles is zero indicates a composition in which the silica fine particles are not added as in Comparative Example 1, and thus the solvent evaporation step is omitted as in Comparative Example 1. .
• the example in which the addition amount of the silane compound is zero indicates a composition in which unmodified colloidal silica is added as it is as in Comparative Example 2.
• Curable composition (thermosetting system; not gelled) (X-1) to (X-7), (X-10) to (X-12), (Y-1), (Y-3) , (Y-4), (Y-7), (Y-14), (Y-16), (Y-17), (Y-19), (Y-20) on different glass substrates, respectively.
• a coating film was formed by coating so that the thickness of the cured film was about 500 to 550 ⁇ m or about 200 ⁇ m, and the coating film was cured by heat treatment at 130 ° C. for 30 minutes.
• Curable composition (photocuring system; not gelled) (X-8), (X-9), (X-13) to (X-16), (Y-8), (Y-12) , (Y-13), (Y-23), (Y-26), (Y-30) to (Y-32) on a separate glass substrate, the thickness of the cured film is about 500 to 550 ⁇ m.
• a coating film was formed by coating to a thickness of about 200 ⁇ m, and the coating film was cured by exposing the coating film at an intensity of 5 J / cm 2 using an exposure apparatus incorporating an ultrahigh pressure mercury lamp.
• Viscosity The viscosity of each curable composition was measured at 25 ° C. using a B-type viscometer DV-III ULTRA (manufactured by BROOKFIELD). The curable composition has better handling properties as the viscosity is moderately low.
• the shrinkage ratio of the curable composition to which a photopolymerization initiator is added is the same as that of the curable composition.
• the film was coated (conditions for the thickness of the cured film to be about 500 ⁇ m), and cured in a nitrogen atmosphere under the same exposure conditions as in the above ⁇ Production of cured film>.
• the film thickness before and after curing was measured with a film thickness meter (F20-NIR, manufactured by Film Metrics Co., Ltd.), and the shrinkage was determined by the following formula. The lower the shrinkage rate, the better the moldability of the curable composition.
• the shrinkage ratio of the curable composition to which the thermal polymerization initiator is added is the density specific gravity meter (DA-650; Kyoto) Measured by Electronic Industries Co., Ltd., and the specific gravity after curing under the conditions described in the column of ⁇ Production of cured film> was measured by an automatic hydrometer (DMA-220H; manufactured by Shinko Denshi Co., Ltd.). Obtained by the formula.
• the unit of numerical values of the composition of the silica fine particles and the silane compounds (A1), (A2) and (meth) acrylates (B1), (B2) is parts by mass.
• the amount of the silane compounds (A1) and (A2) is the amount of the silane compound used for the surface modification with respect to 100 parts of the silica fine particles before the surface modification.
• the total amount with the amount of acrylate (B2) is set to 100 parts.
• the silica fine particles have a particle size of 10 nm because of isopropyl alcohol-dispersed colloidal silica (silica fine particle content of 30 mass%, average particle size of 10 to 20 nm, trade name: Snowtech IPA-ST; Nissan Chemical Industries, Ltd.
• the particle size is 200 nm because of methyl ethyl ketone-dispersed colloidal silica (silica fine particle content 40 mass%, average particle size 200 nm, trade name: Snowtech MEK-ST-2040; Nissan Chemical Industries, Ltd.)
• the particle diameter of 500 nm is isopropyl alcohol-dispersed spherical silica (silica fine particle content 60 mass%, average particle diameter 500 nm, trade name: Admafine SC-2050; manufactured by Admatechs Co., Ltd.) is there.
• TMPTA Trimethylolpropane triacrylate (Trifunctional monomer: Nippon Kayaku Co., Ltd.)
• APG700 Polypropylene glycol (# 700) diacrylate (bifunctional monomer; trade name: NK ester APG-700; manufactured by Shin-Nakamura Chemical Co., Ltd.)
• ADMA adamantyl methacrylate (monofunctional monomer; manufactured by Osaka Organic Chemical Industry Co., Ltd.)
• IRR214K dimethylol tricyclodecane diacrylate (bifunctional monomer; trade name: IRR214-K; manufactured by Daicel Cytec Co., Ltd.))
• X-1 to (X-7) have an appropriate viscosity, excellent handling properties, and small curing shrinkage.
• the cured products obtained by thermal polymerization of the curable compositions (X-1) to (X-7) have a small average linear expansion coefficient and a high light transmittance.
• the cured product obtained from the curable composition (Y-1) containing no silica fine particles generally has a mean line more than the cured product obtained from the curable compositions (X-1) to (X-7). High expansion coefficient and high shrinkage.
• the curable composition (Y-3) obtained by surface modification of silica fine particles with only PhS has a significantly higher viscosity than the curable composition (X-1) using only MOS. Further, the transmittance of the cured product obtained from the curable composition (Y-3) is also lower than the transmittance of the cured product obtained from the curable composition (X-1). Further, the curable composition (Y-4) obtained by modifying the surface of silica fine particles with only MPS has a higher viscosity and a linear expansion coefficient than the curable composition (X-1) using only MOS. The shrinkage rate was also inferior.
• the curable composition (X-2) in which the silica fine particles were surface-modified with MOS and PhS and the curable composition (Y-5) in which the silica fine particles were surface-modified with MPS and PhS the curable composition (Y-5) gelled.
• the curable composition (Y-6) with increased silica fine particles was also gelled. Therefore, by modifying the surface of the silica fine particles with the silane compound (A1), the dispersion stability can be improved, the viscosity can be reduced, and a curable composition excellent in handling properties can be obtained.
• the cured product of the curable composition (X-7) is more curable composition ( The shrinkage is lower than that of the cured product of Y-7). Therefore, a curable composition having high moldability can be obtained by surface-modifying silica fine particles with the silane compound (A1).
• the curable compositions (X-8) and (X-9) have an appropriate viscosity, excellent handling properties, and small curing shrinkage. Furthermore, the cured product obtained by photopolymerizing the curable compositions (X-8) and (X-9) has a small average linear expansion coefficient and a high light transmittance. On the other hand, the cured product obtained from the curable composition (Y-8) that does not contain silica fine particles has an average linear expansion higher than the cured products obtained from the curable compositions (X-8) and (X-9). High coefficient and high shrinkage. Therefore, the heat resistance of the cured product is improved by modifying the surface of the silica fine particles with the silane compound (A1).
• the curable composition (Y-9) in which the silica fine particles were not surface-modified was gelled. Accordingly, the surface stability of the silica fine particles with the silane compound (A1) improves the dispersion stability of the silica fine particles.
• the curable compositions (Y-10) and (Y-11) obtained by surface-modifying silica fine particles only with MPS or VTS alone gelled. Therefore, by modifying the surface of the silica fine particles with the silane compound (A1), the dispersion stability can be improved, the viscosity can be reduced, and a curable composition excellent in handling properties can be obtained.
• a curable composition Comparing the curable composition (X-9) in which silica fine particles were surface-modified with MOS and PhS and the curable composition (Y-12) in which silica fine particles were surface-modified with VTS and PhS, a curable composition ( The transmittance of the cured product obtained from X-9) is higher than the transmittance of the curable composition (Y-12). Comparing the curable composition (X-9) in which silica fine particles were surface-modified with MOS and PhS and the curable composition (Y-13) in which silica fine particles were surface-modified with MPS and PhS, a curable composition ( The average linear expansion coefficient of the cured product of X-9) is lower than the average linear expansion coefficient of the cured product of the curable composition (Y-13). Therefore, the surface modification of the silica fine particles with the silane compound (A1) improves the heat resistance and transparency of the cured product.
• the curable composition (X-10) has an appropriate viscosity, is excellent in handling properties, and has a small curing shrinkage. Furthermore, a cured product obtained by thermal polymerization of the curable composition (X-10) has a high light transmittance. On the other hand, the curable composition (Y-14) containing no silica fine particles has a higher shrinkage than the cured product of the curable composition (X-10). Therefore, a curable composition having a low shrinkage ratio and excellent moldability can be obtained by blending silica fine particles surface-modified with the silane compound (A1).
• the curable composition (Y-15) that did not modify the surface of the silica fine particles was gelled. Therefore, by modifying the surface of the silica fine particles with the silane compound (A1), the dispersion stability can be improved, the viscosity can be reduced, and a curable composition excellent in handling properties can be obtained.
• a curable composition (X-10) Comparing the curable composition (X-10) in which silica fine particles were surface-modified with MOS and PhS and the curable composition (Y-16) in which silica fine particles were surface-modified with MPS and PhS, a curable composition ( X-10) has lower viscosity and lower shrinkage. Therefore, by modifying the surface of the silica fine particles with the silane compound (A1), the dispersion stability can be improved, the viscosity can be reduced, and a curable composition excellent in handling properties can be obtained, the shrinkage rate can be reduced, and the molding can be performed. Increases nature.
• a cured product obtained by thermal polymerization of the curable composition (X-11) has a low average linear expansion coefficient and a high light transmittance.
• the curable composition (Y-17) containing no silica fine particles has a higher shrinkage than the curable composition (X-11).
• the average linear expansion coefficient of the cured product is high. Therefore, a curable composition having a low shrinkage ratio and excellent moldability can be obtained by blending silica fine particles surface-modified with the silane compound (A1).
• the curable composition (Y-18) that did not modify the surface of the silica fine particles was gelled. Therefore, by modifying the surface of the silica fine particles with the silane compound (A1), the dispersion stability can be improved, the viscosity can be reduced, and a curable composition excellent in handling properties can be obtained.
• a curable composition Comparing the curable composition (X-11) in which silica fine particles were surface-modified with MOS and PhS and the curable composition (Y-19) in which silica fine particles were surface-modified with MPS and PhS, a curable composition ( The cured product of X-11) has a lower average linear expansion coefficient than the cured product of the curable composition (Y-19). Therefore, the heat resistance is improved by modifying the surface of the silica fine particles with the silane compound (A1).
• the curable composition (X-12) has an appropriate viscosity and is excellent in handling properties.
• a cured product obtained by thermal polymerization of the curable composition (X-12) has a low average linear expansion coefficient and a high light transmittance.
• the curable composition (Y-20) containing no silica fine particles has a higher shrinkage than the curable composition (X-11).
• the average linear expansion coefficient of the cured product is high. Therefore, by blending silica fine particles surface-modified with the silane compound (A1), a curable composition having a low shrinkage and excellent moldability is obtained, and the heat resistance of the cured product is further improved.
• the curable composition (Y-21) which does not modify the surface of the silica fine particles was gelled. Therefore, by modifying the surface of the silica fine particles with the silane compound (A1), the dispersion stability can be improved, the viscosity can be reduced, and a curable composition excellent in handling properties can be obtained.
• the curable composition (Y-22) in which silica fine particles were surface-modified with MPS and PhS was gelled. Therefore, by modifying the surface of the silica fine particles with the silane compound (A1), the dispersion stability can be improved, the viscosity can be reduced, and a curable composition excellent in handling properties can be obtained.
• the curable composition (X-13) has an appropriate viscosity, excellent handling properties, and small curing shrinkage.
• a cured product obtained by photopolymerizing the curable composition (X-13) has a high light transmittance.
• a cured product of the curable composition (Y-23) not containing silica fine particles was brittle and easily cracked, and thus was not suitable for measuring the average linear expansion coefficient. Therefore, a curable composition having excellent moldability can be obtained by blending silica fine particles surface-modified with the silane compound (A1).
• the curable composition (Y-24) which does not modify the surface of the silica fine particles was gelled. Therefore, by modifying the surface of the silica fine particles with the silane compound (A1), the dispersion stability can be improved, the viscosity can be reduced, and a curable composition excellent in handling properties can be obtained.
• the curable composition (Y-25) in which silica fine particles were surface-modified with MPS and PhS was gelled. Therefore, by modifying the surface of the silica fine particles with the silane compound (A1), the dispersion stability can be improved, the viscosity can be reduced, and a curable composition excellent in handling properties can be obtained.
• the curable compositions (X-14) to (X-16) have an appropriate viscosity, are excellent in handling properties, and have small curing shrinkage.
• the curable composition (Y-26) containing no silica fine particles has a higher shrinkage than the curable composition (X-14).
• the cured product of the curable composition (Y-26) has a higher average linear expansion coefficient than the cured product of the curable composition (X-14). Therefore, a curable composition having excellent moldability is obtained by blending silica fine particles surface-modified with the silane compound (A1), and the heat resistance of the cured product is improved.
• the curable compositions (Y-27) to (Y-29) in which the silica fine particles were not surface-modified were gelled. Therefore, by modifying the surface of the silica fine particles with the silane compound (A1), the dispersion stability can be improved, the viscosity can be reduced, and a curable composition excellent in handling properties can be obtained.
• the viscosity of the curable composition (Y-30) obtained by surface-modifying silica fine particles with MPS and PhS is significantly higher than that of the curable composition (X-14).
• the cured product of the curable composition (Y-31) obtained by surface-modifying silica fine particles having an average particle diameter of about 200 nm with MPS and PhS has a higher average linear expansion coefficient than the cured product of the curable composition (X-15).
• the curable composition (Y-32) obtained by surface-modifying silica fine particles having an average particle diameter of about 500 nm with MPS and PhS has a higher shrinkage than the curable composition (X-16).
• the dispersion stability can be improved, the viscosity can be reduced, and a curable composition having excellent handling properties can be obtained, and the shrinkage rate can be reduced and molded. Improves the heat resistance of the cured product.
• a cured product obtained by curing the curable composition of the present invention is excellent in transparency, heat resistance, and low linear expansion.
• This cured product is a transparent plate, optical lens, optical disk substrate, plastic substrate for liquid crystal display element, substrate for color filter, plastic substrate for organic EL display element, substrate for solar cell, touch panel, optical element, optical waveguide, LED sealing It can be suitably used for optical materials such as materials and electronic materials.

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